The continuous exploration of new analogs of calixarenes and pillararenes unlocks infinite opportunities in supramolecular chemistry and materials. In this work, we introduce a new class of macrocycle, phenyl‐extended resorcin[4]arenes (ExR4), a unique and innovative design that incorporates unsubstituted phenylene moieties into the resorcin[4]arene scaffold. Single‐crystal analysis reveals a chair‐like conformation for per‐methylated ExR4 (Me‐ExR4) and a twisted "figure‐of‐eight" shaped conformation for per‐hydroxylated ExR4 (OH‐ExR4). Notably, OH‐ExR4 demonstrates exceptional adsorption capability toward I3− ions in an aqueous solution, with a rapid kinetic rate of 1.18×10‐2 g·mg‐1·min‐1. Furthermore, OH‐ExR4 shows excellent recyclability and potential as a stationary phase in column setups. The discovery of ExR4 opens up new avenues for constructing new macrocycles and inspires further research in functional adsorption materials for water pollutant removal.